Dithiolene metal complex colorless IR absorbers

ABSTRACT

The invention relates to the use of compounds of formulae (I) and/or (II) as colorless IR absorbers wherein M is Ni, Pd, Pt, Au, Ir, Fe, Zn, W, Cu, Mo, In, Mn, Co, Mg, V, Cr or Ti, X 1 , X 2  and X 3  are each independently of the others sulfur or oxygen, R 1 , R 2 , R 3 , R 4 , R 5  and R 6  are each independently of the others hydrogen, NR 7 R 8 , unsubstituted or substituted C 1 -C 18 alkyl, C 1 -C 18  alkyl wherein the alkylene chain is interrupted with oxygen, unsubstituted or substituted C 1 -C 18 alkenyl, unsubstituted or substituted aryl, unsubstituted or substituted arylalkyl or unsubstituted or substituted heteroarylalkyl, R 7  and R 8 , each independently of the other, being unsubstituted or substituted C 1 -C 18 alkyl, unsubstituted or substituted aryl, unsubstituted or substituted arylalkyl or unsubstituted or substituted heteroarylalkyl, a further IR absorber optionally being added to the compounds of formulae (I) and (II). The invention relates also to novel dithiolene compounds of formulae (I) and (II) wherein X 1  is oxygen and X 2  and X 3  are oxygen or sulfur. The invention relates furthermore to novel dithiolene compounds of formulae (I) and (II) wherein R 1  to R 6  are NR 7 R 8 .

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional of U.S. patent application Ser. No. 12/520,889,filed Jun. 23, 2009, which is the U.S. national phase of InternationalApplication No. PCT/EP2007/064102, filed Dec. 18, 2007, which claims thebenefit of European Patent Application No. 07100657.1, filed Jan. 17,2007.

The invention relates to the use of specific dithiolene metal complexesas colorless IR absorbers. The invention relates also to noveldithiolene metal complexes.

Colorless, or at least barely colored, IR absorbers meet a significanttechnical need in a wide range of applications, such as securityprinting (bank notes, credit cards, identity cards, passports etc.),invisible and IR readable bar codes, the laser-welding of plastics, thecuring of surface-coatings using IR radiators, the drying and curing ofprint, the fixing of toners on paper, optical filters for PDPs (plasmadisplay panels), laser marking, the heating of plastics preforms etc.

Several classes of IR absorbers are known, such as, for example,quinone-diimmonium or aminium salts, polymethines (e.g. cyanines,squaraines, croconaines), phthalocyanines and naphthalocyanines,dithiolene and other metal complexes. Newer structures, such as, forexample, quaterrylene diimides, have also recently become known.

Also known, besides those organic substances, are inorganic substancessuch as, for example, lanthanum hexaboride, indium tin oxide (ITO),antimony tin oxide (ATO) in nano-particulate form and coated micamaterials (“Lazerflair” from Merck).

Notwithstanding that large number of known compound classes andstructures, as yet no IR absorbers have become known that aresatisfactory from the technical standpoint. Especially in respect of“colorlessness”, that is, minimum inherent color, no truly satisfactorysolutions are known that simultaneously meet the other technicalstability requirements (heat stability and/or light stability). IRabsorbers, for example for security printing, are available, forexample, from “American Dye Source”, but virtually all of them have anabsorption in the VIS range of the spectrum (from 400 to 700 nm).

It has now been found, surprisingly, that a class of heterocyclicdithiolene metal complexes, known per se, is able to meet thoserequirements. Especially in respect of colorlessness, these compoundsare appreciably superior to the known IR absorbers—while simultaneouslymeeting other technical requirements, such as, for example, goodfastness to light (for security printing) or good heat stability whenincorporated into plastics material (laser-welding of plastics).

The invention accordingly relates to the use of compounds of formula Iand/or II as colorless IR absorbers

wherein

M is Ni, Pd, Pt, Au, Ir, Fe, Zn, W, Cu, Mo, In, Mn, Co, Mg, V, Cr or Ti,

X₁, X₂ and X₃ are each independently of the others sulfur or oxygen,

R₁, R₂, R₃, R₄, R₅ and R₆ are each independently of the others hydrogen,NR₇R₈, unsubstituted or substituted C₁-C₁₈alkyl, C₁-C₁₈ alkyl whereinthe alkylene chain is interrupted with oxygen, unsubstituted orsubstituted C₁-C₁₈alkenyl, unsubstituted or substituted aryl,unsubstituted or substituted arylalkyl or unsubstituted or substitutedheteroarylalkyl, R₇ and R₈, each independently of the other, beingunsubstituted or substituted C₁-C₁₈alkyl, unsubstituted or substitutedaryl, unsubstituted or substituted arylalkyl or unsubstituted orsubstituted heteroarylalkyl,

a further IR absorber optionally being added to the compounds offormulae I and II.

Preference is given to compounds of formula I wherein the metal M is Ni,Pd or Pt. (claim 2)

If the substituents R₁ to R₆ or R₁ to R₄ are C₁-C₁₈alkyl radicals theyare preferably unsubstituted C₁-C₁₈alkyl radicals, more preferablyC₁-C₈alkyl radicals, including straight-chain and branched and alsocyclic alkyl radicals. The following may be mentioned as examples:propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-hexyl,2-ethylhexyl, n-octyl, cyclopentyl, cyclohexyl.

If the substituents R₁ to R₆ or R₁ to R₄ are C₁-C₁₈alkyl radicalswherein the alkylene chain is interrupted with oxygen, they arepreferably —(CH₂)_(n)—[O—(CH₂)_(m)]_(k)—OCH₃ with n=2-6, m=2 or 3,k=1-6.

If the substituents R₁ to R₆ or R₁ to R₄ are C₁-C₁₃alkenyl radicals theyare preferably unsubstituted C₁-C₁₈alkenyl radicals, more preferablyC₁-C₆alkenyl radicals. Examples may be vinyl or allyl.

If the substituents R₁ to R₆ or R₁ to R₄ are aryl groups, they arepreferably unsubstituted aryl groups, for example, phenyl, naphthyl,anthryl or phenanthryl groups.

If the substituents R₁ to R₆ or R₁ to R₄ are arylalkyl groups, they arepreferably unsubstituted arylalkyl groups, for example,—(CH₂)_(q)-phenyl with q=1-6, especially benzyl, ethylphenyl,propylphenyl.

If the substituents R₁ to R₆ or R₁ to R₄ are heteroarylalkyl radicalsthey are preferably unsubstituted heteroarylalkyl radicals which denotesthat a heteroaromatic ring is bonded directly to an alkyl group. Theheteroaromatic ring is, for example, imidazolyl, pyridyl, thienyl,furyl, thiazolyl, indolyl, quinolinyl, pyrazolyl, pyrazyl, pyridazyl orpyrimidinyl.

The substituents R₁ to R₆ or R₁ to R₄ are preferably unsubstitutedC₁-C₁₈alkyl, —(CH₂)_(n)—[O—(CH₂)_(n)]_(k)—OCH₃ with n=2-6, m=2 or 3,k=1-6, unsubstituted C₁-C₁₈alkenyl, unsubstituted arylalkyl or—N(C₁-C₆alkyl)₂.

The substituents R₇ and R₈ are preferably C₁-C₆alkyl radicals.

In a preferred embodiment compounds of the formula I are used ascolorless IR absorber

wherein

M is Ni, Pd, Pt,

X₁, X₂ and X₃ are each independently of the others sulfur or oxygen,

R₁, R₂, R₃, R₄ are each independently of the others —N(C₁-C₆alkyl)₂,unsubstituted C₁-C₈alkyl, —(CH₂)_(n)—[O—(CH₂)_(m)]_(k)—OCH₃ with n=2-6,m=2 or 3, k=1-6; vinyl or allyl, —(CH₂)_(q)-phenyl with q=1-6. (Claim 3)

Of particular interest are the structures Ia to Ih.

(Claim 4)

Colorless IR absorbers can be used in all fields of application thatdepend on the IR absorber's remaining invisible. The following uses maybe mentioned by way of example: security printing (bank notes, creditcards, identity cards, passports etc.), invisible and IR readable barcodes, the laser-welding of plastics, the curing of surface-coatingsusing IR radiators, the drying and curing of print, the fixing of tonerson paper, laser marking (plastics materials, paper, wood etc.) and theheating of plastics preforms. (Claim 5)

An especially suitable field of application is the use of the compoundsof formula I and/or II in security printing and in the laser-welding ofplastics material. (Claim 6)

In another embodiment the compounds of formulae I and II are used insecurity printing and printing of bar codes. (claim 7)

The IR absorbers of formulae I and II can also be in the form ofmixtures with further known IR absorbers, especially mixtures withpolymethines (cyanines, squaraines and croconaines). Such IR absorbermixtures are suitable especially for security printing. (claim 8)

Examples of preferred polymethines are listed in the following Tables:

Cyanines

Squaraines

Croconaines

The IR absorbers are used in a concentration of from 10 ppm to 10%,preferably 100 ppm to 2% depending on the chosen application.

The laser welding is preferably carried out using an ND:YAG laser at1064 nm or using a diode laser at 980 nm or 940 nm, and theconcentration of IR absorber is, for example, from 5 to 500 ppm,preferably from 10 to 100 ppm.

In laser welding, plastics components are welded to one another. Thedithiolenes according to the invention are suitable especially forwelding transparent plastics materials, such as polypropylene,polyvinylbutyral, polyamide, polycarbonate, polycarbonate-polyethyleneterephthalate blends, polycarbonate-polybutylene terephthalate blends,polycarbonate-acrylonitrile-styrene-acrylonitrile copolymer blends,polycarbonate-acrylonitrile-butadiene-styrene copolymer blends,polymethyl methacrylate-acrylonitrile-butadiene-styrene copolymer blends(MABS), polyethylene terephthalate, polybutylene terephthalate,polymethyl methacrylate, polybutyl acrylate, polymethylmethacrylate-polyvinylidene difluoride blends,acrylonitrile-butadiene-styrene copolymers (ABS), styrene-acrylonitrilecopolymers (SAN) and polyphenylene sulfone and also mixtures thereof.

Especially advantageous in welding is the use of two identicallytransparent plastics workpieces, for examplecolorless-transparent/colorless-transparent orcolored-trans-parent/colored-transparent.

In security printing, the IR absorber is added to the printing ink.Suitable printing inks are water-based, oil-based or solvent-basedprinting inks, based on pigment or dye, for inkjet printing,flexographic printing, screen printing, intaglio printing, offsetprinting, laser printing or letterpress printing and for use inelectrophotography.

The invention relates also to novel dithiolene compounds of formulae Iand II wherein

M is Ni, Pd, Pt, Au, Ir, Fe, Zn, W, Cu, Mo, In, Mn, Co, Mg, V, Cr or Ti,

X₁ is oxygen and X₂ and X₃ are oxygen or sulfur,

R₂, R₃, R₄, R₅ and R₆ are each independently of the others hydrogen,NR₇R₈, unsubstituted or substituted C₁-C₁₈alkyl, C₁-C₁₈ alkyl whereinthe alkylene chain is interrupted with oxygen, unsubstituted orsubstituted C₁-C₁₈alkenyl, unsubstituted or substituted aryl,unsubstituted or substituted arylalkyl or unsubstituted or substitutedheteroarylalkyl, R₇ and R₈, each independently of the other, beingunsubstituted or substituted C₁-C₁₈alkyl, unsubstituted or substitutedaryl, unsubstituted or substituted arylalkyl or unsubstituted orsubstituted heteroarylalkyl. (Claim 9)

Those compounds are obtained from the corresponding sulfur compounds(X₁, X₂, X₃═S) by oxidation with a suitable solvent or as described bythe examples.

The following compounds may be mentioned by way of example:

The invention relates also to novel dithiolene compounds of formulae Iand II wherein

M is Ni, Pd, Pt, Au, Ir, Fe, Zn, W, Cu, Mo, In, Mn, Co, Mg, V, Cr or Ti,

X₁, X₂ and X₃ are each independently of the others sulfur or oxygen,

R₁, R₂, R₃, R₄, R₅ and R₆ are NR₇R₈, wherein R₇ and R₈ are eachindependently of the other unsubstituted or substituted C₁-C₁₈alkyl,unsubstituted or substituted aryl, unsubstituted or substitutedarylalkyl or unsubstituted or substituted heteroarylalkyl. (claim 10).

Preferably —NR₇R₈ is —N(C₁-C₆alkyl)₂

The following compounds Ic and Id may be mentioned by way of example:

The novel dithiolene compounds, like the known dithiolene compounds, aresuitable for use in security printing (bank notes, credit cards,identity cards, passports etc.), invisible and IR readable barcodes, thelaser-welding of plastics, the curing of surface-coatings using IRradiators, the curing and drying of print, the fixing of toners onpaper, laser marking (plastics, paper, wood etc.) and the heating ofplastics preforms etc.

Additionally, the novel dithiolene compounds of formulae I and II aresuitable for use as optical filters for plasma display panels (PDPs).For this application absorption below 1000 nm, especially around 900 nm,is of special interest.

EXAMPLES Example 1

Preparation of

The compound is known from J. Chem. Soc., Dalton Trans 1998, 3731-3736,and its preparation is described therein.

1,3-Diisopropyl-4,5-dioxo-imidazoline-2-thione is reacted under refluxconditions with metallic nickel and Lawesson's reagent

in chlorobenzene.

Absorption maximum (chloroform): 1001 nm (79 000)

Example 2

Preparation of

Reaction is carried out analogously to Example 1, with platinumdichloride and Lawesson's reagent.

Absorption maximum (chloroform): 1000 nm (113 000).

Example 3a

Preparation of

12.26 parts of N,N-dimethylhydrazine are added at room temperature, withstirring, to a solution of 7.65 parts of carbon disulfide in 250 partsof dichloroethane. The temperature is then increased to 40° C. andstirring is carried out for 16 hours at that temperature to complete thereaction. The temperature is subsequently increased to 80° C. for onehour.

A further 750 parts of dichloroethane are then added, and 13.88 parts ofoxalyl chloride (dissolved in a small amount of dichloroethane) areadded dropwise over a period of 90 minutes. The reaction mixture is thenheated to reflux and maintained at reflux for 2 hours, after which it isconcentrated and the yellow crystals are filtered off and washed with asmall amount of dichloroethane. After drying, 14 parts of product havingthe structure indicated above are obtained.

Example 3b

Preparation of

0.333 part of platinum dichloride is added to a solution of 0.541 partof the product from example 3a and 1.085 parts of Lawesson's reagent in50 parts of toluene. The reaction mixture is maintained at 110° C. for90 minutes and filtered while hot, and 500 parts of n-hexane are addedto the filtrate after cooling. The resulting precipitate is filtered offand dried, yielding 0.5 part of product (absorption maximum 994 nm).

Example 4

The procedure is analogous to that in the previous examples, except thatthe metal used is molybdenum, thus yielding the corresponding 1:3molybdenum complex:

Example 5

Preparation of

The compound from Example 2 is oxidised with atmospheric oxygen indichloromethane at reflux temperature to form the corresponding oxocompound. Its absorption maximum is found at 968 nm.

Example 6a

Preparation of

29.14 parts of 1,3-di-n-propyl-urea are dissolved in 300 parts oftoluene at 40° C. Over a period of 40 minutes 27.18 parts of oxalylchloride are added at 80° C. to the stirred solution. After a furtherhour of stirring at 100° C. the solution is evaporated at 60° C. todryness: 36.8 parts of the product are obtained.

Example 6b

Preparation of

1.59 parts of the product from Example 6a, 1.06 parts of platinumdichloride and 3.47 parts of Lawesson's reagent are heated to 110° C.under nitrogen in 100 parts of toluene. After 45 minutes reaction timethe dark solution is cooled down to −10° C. and the precipitation isfiltered off, washed with ethanol and some acetone. For purification thecrude product is dissolved in dichloromethane and precipitated slowly byaddition of methanol. Dark blue crystals are collected by filtration.The absorption maximum of the product is found at 900 nm (chloroform).

Example 7

Preparation of

Proceeding analogously to Example 6b but using palladium chlorideinstead of platinum chloride the corresponding palladium complex with anabsorption maximum of 921 nm is obtained.

Example 8

Preparation of

Proceeding analogously to Example 6b but using metallic nickel insteadof platinum chloride the corresponding nickel complex with an absorptionmaximum of 891 nm is obtained.

Example 9 to 24

Compounds of Examples 9 to 24 (structures given in the table below) areobtained by analogous procedures as described in Examples 1 to 8:

Example  9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

Application Examples Example A1 (Security Printing)

11.9 parts of vinyl chloride, 2.1 parts of vinyl acetate, 10 parts ofethoxypropanol, 75.5 parts of methyl ethyl ketone and 0.5 part of theproduct from Example 1 are shaken together with 150 g of glass beads for30 minutes in a Skandex mixer.

The resulting printing ink is applied to contrast paper using a doctorblade (film thickness when damp: 6 μm). The print is visually colorless,but is clearly visible in the IR range using an IR-viewing device(cut-off filter 715 nm). The fastness to light is excellent.

Example A2 (Security Printing)

By proceeding as indicated in Example A1 but using the IR absorber fromExample 2, there accordingly is likewise obtained a colorless printhaving excellent fastness to light, which is clearly visible in theinfrared range using an IR-viewing device.

Example A3 (Laser-Welding of Plastics Material)

Using an injection-moulding machine, the IR absorber from Example 1 isincorporated into a polycarbonate disc having a thickness of 2 mm(concentration: 100 ppm). Using an Nd:YAG laser, the resulting,virtually colorless disc is welded at a power of 30 watt and a rate ofadvance of 20 mm/s to a second 1 mm-thick pure polycarbonate disc notcontaining IR absorber. The resulting weld is characterised by anexcellent bond, unchanged transparency, no melt irruptions and nobubbling. Under heavy mechanical loading, breakage of the discs does notoccur at the welded seam.

Example A4 (Laser-Welding of Plastics Material)

By proceeding as indicated in Example A3 but using the IR absorber fromExample 2, a virtually colorless polycarbonate disc is likewise obtainedwhich has excellent welding properties. The resulting weld has unchangedtransparency, the welding leaves no melt irruptions or bubbling and thestrength of the weld is excellent.

Examples A5 and A6

By proceeding as indicated in Examples A3 and A4 but, instead of usingan Nd:YAG laser (1064 nm), using a diode laser having an emissionwavelength of 980 nm, similarly good results to those described inExamples A3 and A4 are obtained.

Examples A7 and A8

By proceeding as indicated in Examples A3 and A4 but, instead of usingan Nd:YAG laser (1064 nm), using a diode laser having an emissionwavelength of 940 nm, a comparably good weld is obtained at a laserpower of 80 watt.

Example A9

By proceeding as indicated in Example A3, but using polypropylene discshaving a thickness of 1.5 mm, the welds obtained are likewise very good.

The invention claimed is:
 1. Compounds of formulae I and/or II

wherein M is Ni, Pd, Pt, Au, Ir, Fe, Zn, W, Cu, Mo, In, Mn, Co, Mg, V,Cr or Ti, X₁ is oxygen, X₂ and X₃ are each independently of the othersulfur or oxygen, R₁, R₂, R₃, R₄, R₅ and R₆ are each independently ofthe others hydrogen, NR₇R₈, unsubstituted or substituted C₁-C₁₈alkyl,C₁-C₁₈ alkyl wherein the alkylene chain is interrupted with oxygen,unsubstituted or substituted C₁-C₁₈alkenyl, unsubstituted or substitutedaryl, unsubstituted or substituted arylalkyl or unsubstituted orsubstituted heteroarylalkyl, R₇ and R₈, each independently of the other,being unsubstituted or substituted C₁-C₁₈alkyl, unsubstituted orsubstituted aryl, unsubstituted or substituted arylalkyl orunsubstituted or substituted heteroarylalkyl.
 2. Compounds of formulae Iand/or II

wherein M is Ni, Pd, Pt, Au, Ir, Fe, Zn, W, Cu, Mo, In, Mn, Co, Mg, V,Cr or Ti, X₁, X₂ and X₃ are each independently of the others sulfur oroxygen, R₁, R₂, R₃, R₄, R₅ and R₆ are NR₇R₈, wherein R₇ and R₈ are eachindependently of the other unsubstituted or substituted C₁-C₁₈alkyl,unsubstituted or substituted aryl, unsubstituted or substitutedarylalkyl or unsubstituted or substituted heteroarylalkyl.
 3. A compoundselected from the group consisting of


4. Optical filters for plasma display panels incorporating the compoundsof formula I or II according to claim
 1. 5. Compounds of formulae I

wherein M is Ni, Pd, or Pt, X₁ is oxygen, X₂ is sulfur or oxygen, R₁,R₂, R₃, and R₄, are each independently of the others hydrogen, NR₇R₈,unsubstituted C₁-C₁₈alkyl, C₁-C₁₈alkyl wherein the alkylene chain isinterrupted with oxygen, unsubstituted C₁-C₁₈alkenyl, R₇ and R₈, eachindependently of the other, being unsubstituted C₁-C₁₈alkyl. 6.Compounds of formulae I

wherein M is Ni, Pd, or Pt, X₁ and X₂ are each independently of theother sulfur or oxygen, R₁, R₂, R₃, and R₄, are NR₇R₈, wherein R₇ and R₈are each independently of the other unsubstituted C₁-C₁₈alkyl.